Modified Catalyst and Use of This Catalyst for the Conversion of Synthesis Gas to Hydrocarbons

ABSTRACT

The present invention relates to a process for the conversion of synthesis gas to hydrocarbons in the presence of a modified supported Fischer-Tropsch catalyst composition.

The present invention relates to the conversion of synthesis gas tohydrocarbons. In particular, it relates to the conversion of synthesisgas to C5+ hydrocarbons particularly suitable for use as liquid motorfuels.

It is well known that synthesis gas, i.e., hydrogen and carbon monoxide,can be converted to hydrocarbons in the presence of a variety oftransition metal catalysts. Thus, certain-Group VIII metals,particularly iron, cobalt, ruthenium and nickel, are known to catalysethe conversion of CO and hydrogen, also referred to as syngas, tohydrocarbons. Such metals are commonly called Fischer-Tropsch catalysts.While the use of nickel preferentially produces methane upon conversionof syngas; the use of iron, cobalt and ruthenium tends to producehydrocarbon mixtures consisting of hydrocarbons having a larger carbonnumber than methane. At higher reaction temperatures, allFischer-Tropsch catalysts tend to produce gaseous hydrocarbons, and itis readily feasible to select processing conditions to produce methaneas the principal product. At lower temperatures, and usually at higherpressures, however, iron, cobalt and ruthenium produce hydrocarbonmixtures consisting of larger hydrocarbons. The products usually containvery long straight-chain hydrocarbon molecules that tend to precipitateas wax. Such wax material, boiling well beyond the boiling range ofmotor fuels, typically constitutes a significant fraction of the productproduced in such catalytic conversion operations. Fischer-Tropschcatalysts, therefore, have not been advantageously employed in theproduction of liquid hydrocarbon motor fuels, since they have commonlyproduced either principally gaseous hydrocarbons, on the one hand, orhydrocarbons containing an unacceptably large amount of wax on theother. In addition, the gasoline boiling hydrocarbon fraction producedhas an unacceptably low octane number.

Another difficulty present in the production of liquid motor fuels,particularly those boiling in the gasoline boiling range, by theconversion of syngas in the presence of Fischer-Tropsch metal catalystsis the tendency of such Fischer-Tropsch metals to characteristicallyproduce straight chain hydrocarbons consisting of a mixture ofn-paraffins and n-olefins. The actual mixture obtained will beunderstood to depend upon the particular metal catalyst and the processconditions employed. In any event, the conversion product will generallycontain only small amounts of mono-branched and almost no multi-branchedhydrocarbons, as well as very little naphthenes and aromatics. Theabsence of branched or aromatic, i.e. cyclic, hydrocarbons in theconversion products results in such products having gasoline fractionsof very low octane number, or O.N. Such fractions are not suitable foruse as gasoline without the addition of further, expensive refiningsteps. The larger n-paraffins produced in the C10-C18 range by suchmetal catalysts are, of course, desirable components for incorporationin jet and diesel fuels. However, the presence of some branched andaromatic hydrocarbons are also desired in such components to enhance thethermal efficiency of the overall process for converting raw syngas tosuch liquid motor fuels and to reduce the pour point of such fuels.

For the reasons above, the development of improved technology for theconversion of syngas to liquid hydrocarbon fuels is desired in the art.Such improved technology would desirably enable such syngas conversionto be carried out with (1) enhanced branching and aromatisation ascompared with the present production of predominately n-paraffins andn-olefins, and (2) enhanced production of desired liquid motor fuels byreducing the formation of methine and of heavy hydrocarbon productsboiling beyond the boiling range of diesel oil. At the same time, thecatalyst composition must have a requisite degree of activity andstability to enable the production of such motor fuels to be carried outin practical commercial operations.

It is an object of the invention, therefore, to provide an improvedprocess and catalyst composition for the conversion of syngas to liquidhydrocarbon motor fuels.

It is another object of the invention to provide a stable catalystcomposition capable of enhancing the conversion of syngas to such liquidfuels.

It is a further object of the invention to provide a process andFischer-Tropsch catalyst composition for producing liquid motor fuelscontaining minimal amounts of methane and of heavy hydrocarbon productsboiling beyond the boiling range of diesel oil.

With these and other objects in mind, the invention is hereinafterdescribed in detail; the novel features thereof being particularlypointed out in the appended claims.

Synthesis gas is converted to liquid motor fuels in the practice of theinvention by the use of a modified catalyst composition containing asupported Fischer-Tropsch metal as a component thereof. The conversionproduct contains minimal amounts of methane and of heavy productsboiling beyond the boiling range of diesel oil.

The objects of the invention are accomplished by modifying a catalystcomposition containing a supported Fischer-Tropsch metal and using it inthe conversion of syngas to liquid hydrocarbons. Contrary to the resultspreviously obtained by the use of unmodified Fischer-Tropsch catalystsfor syngas conversion, the use of such a modified catalyst compositionresults in an advantageous production of liquid motor fuels boiling inthe jet fuel plus diesel oil boiling range. As the modified catalystcomposition is found to have outstanding stability over the course ofcontinuous processing operations, the modified catalyst composition andthe process for its use for syngas conversion, as herein described andclaimed, represent a highly desirable and practical approach to thedesired production of liquid motor fuels boiling in the gasoline, jetfuel and diesel oil boiling range.

The synthesis gas, or syngas, treated in accordance with the practice ofthe invention generally comprises a mixture of hydrogen and carbonmonoxide, although smaller amounts of carbon dioxide, methane, nitrogenand other components may also be present as will be well known to thoseskilled in the art. The syngas may be prepared using any of theprocesses known in the art including partial oxidation of hydrocarbons,steam reforming, gas heated reforming, microchannel reforming (asdescribed in, for example, U.S. Pat. No. 6,284,217 which is hereinincorporated by reference), plasma reforming, autothermal reforming andany combination thereof. A discussion of these synthesis gas productiontechnologies is provided in “Hydrocarbon Processing” V78, N.4, 87-90,92-93 (April 1999) and “Petrole et Techniques”, N. 415, 86-93(July-August 1998). It is also envisaged that the synthesis gas may beobtained by catalytic partial oxidation of hydrocarbons in amicrostructured reactor as exemplified in “IMRET 3: Proceeding of theThird International Conference on Microreaction Technology”, Editor WEhrfeld, Springer Verlag, 1999, pages 187-196. Alternatively, thesynthesis gas may be obtained by short contact time catalytic partialoxidation of hydrocarbonaceous feedstocks as described in EP 0303438.Preferably, the synthesis gas is obtained via a “Compact Reformer”process as described in “Hydrocarbon Engineering”, 2000, 5, (5), 67-69;“Hydrocarbon Processing”, 79/9, 34 (September 2000); “Today's Refinery”,15/8, 9 (August 2000); WO 99/02254; and WO 200023689.

The Fischer-Tropsch process of the invention is preferably carried outat a temperature of 180-280° C., more preferably 190-240° C. TheFischer-Tropsch process of the invention is preferably carried out at apressure of 5-50 bar, more preferably 15-35 bar, generally 20-30 bar.

Preferably, the ratio of hydrogen to carbon monoxide in the synthesisgas is in the range of 20:1 to 0.1:1 by volume and especially in therange of 5:1 to 1:1 by volume e.g. 2:1 by volume.

The modified catalyst composition of the invention, employed asdescribed herein for the conversion of syngas to liquid motor fuels,contains a Fischer-Tropsch metal supported on an appropriate carrier.Various Group VIII metals known to catalyse the conversion of syngas tohydrocarbons, and commonly referred to as Fischer-Tropsch catalysts, maybe employed in the practice of the invention, e.g. iron, cobalt,ruthenium and nickel as well as molybdenum, tungsten, rhenium and thelike. It has been found that, on an overall evaluation basis, the use ofiron and of cobalt as the Fischer-Tropsch metal component of thecatalytic composition is particularly desirable for purposes of theinvention.

The second principal component of the catalyst composition of theinvention is the support which can preferably be chosen amongst alumina,silica, titania, zinc oxide or mixtures thereof. It has been found that,on an overall evaluation basis, the use of zinc oxide as the support ofthe Fischer-Tropsch metal component of the catalytic composition isparticularly desirable for purposes of the invention.

According to a preferred embodiment of the present invention, thecatalyst employed in the process of the present invention is a cobaltsupported catalyst. Preferably the cobalt is supported on an inorganicoxide. Preferred supports include silica, alumina, silica-alumina, theGroup IVB oxides, titania (primarily in the rutile form) and preferablyzinc oxide. The supports generally have a surface area of less thanabout 100 m²/g, suitably less than 50 m²/g, for example, less than 25m²/g or about 5 m²/g.

Usually at least 0.1% cobalt (by weight of support) is present andpreferably about 0.1-20%, and especially 0.5-5 wt %. Promoters may beadded to the catalyst and are well known in the Fischer-Trospch catalystart. Promoters can include ruthenium, platinum or palladium (when notthe primary catalyst metal), aluminium, rhenium, hafnium, cerium,lanthanum and zirconium, and are usually present in amounts less thanthe cobalt (except for ruthenium which may be present in coequalamounts), but the promoter:metal ratio should be at least 1:10.Preferred promoters are rhenium and hafnium. The particulateFischer-Tropsch catalyst may have an average particle size in the range5 to 500 microns, preferably 5 to 100 microns, for example, in the range5 to 40 microns.

The modification of the catalyst composition of the present invention isobtained by using a silylating compound. This silylating compound may beused during the catalyst preparation or during a post-treatment stage.According to a preferred embodiment of the present invention, theprepared catalyst composition containing the supported Fischer Tropschmetal is post-treated with the silylating compound.

The silylating compound used according to the present invention ispreferably chosen amongst organosilicon compound, more preferably chosenamongst trimethyl silicon compounds, most preferably chosen amongsttrimethylsilyl chloride, bis (trimethylsilyl)trifluoroacetamide,N-methyl-N-(trimethylsilyl)trifluoroacetamide, and mixtures thereof.According to a preferred embodiment of the present invention, bis(trimethylsilyl)trifluoroacetamide is used as modifier.

The Applicants have unexpectedly found that the modified catalysts ofthe present invention show an increased activity and a longer catalystlife.

While not wishing to be bound to this theory, the Applicants believethat the use of the organosilicon compound has transformed the catalystin such a way that a water repelling/dispersing functionality has beencreated. Indeed, it is well known that some water is produced in thecourse of the syngas conversion into hydrocarbons and that this water isdetrimental to the activity and lifetime of the Fischer Tropschcatalyst. The exceptional behaviour of the modified catalyst of thepresent invention might thus be the result of the introduction of achemical functionality that has a hydrophobic component in the catalystcomposition, and that this hydrophobic component is able to disperse andrepel produced water from the catalyst so leading to an increase inactivity and longer catalyst life.

The invention is hereinafter described with reference to certainspecific examples that are presented to illustrate various embodiments,but that should not be construed as limiting the scope of the inventionas set forth in the appended claims.

EXAMPLE 1 PREPARATION OF HYDROPHOBIC CATALYST

20 g of B958-30, an Engelhard cobalt based Fischer Tropsch catalystdried at 100° C. or 1 hour then cooled, was weighed into a sealableglass vessel and a derivatization grade silating reagent [Bis(trimethylsilyl)trifluoroacetamide] was added to completely immerse thecatalyst. The vessel was sealed and stored in a refrigerator atapproximately 4° C. overnight. After 16 hours soaking the supernatantliquid was drained from the solid and the tread catalyst allowed toair-dry.

EXAMPLE 2 TESTING OF HYDROPHOBIC CATALYST

10.0 ml (14.5 g) of the treated catalyst was charged to a fixed bedreactor and activated as follows:—

Nitrogen flow at a GHSV=1800 hr−1 was established to the reactor whichwas at ambient temperature and pressure and then the reactor temperaturewas increased at 1° C. per min to 250° C. The pressure in the system wasthat required to overcome the pressure drop across the catalyst bed, theexit gas from the reactor was at atmospheric pressure. When the reactorwas at 250° C., the catalyst was allowed to dwell at this temperaturefor 1 hr before the nitrogen flow was changed to carbon monoxide flowingat the same GHSV. Reduction of the catalyst with carbon monoxide wascontinued for 3.5 hrs before the carbon monoxide flow was stopped andreplaced with the same flow of nitrogen to purge all the reductant gasout of the system. When the system was free of carbon monoxide, the flowwas stopped and replaced by hydrogen flowing at a GHSV=800 hr-1.Hydrogen reduction at 250° C. was continued for 16 hrs before the heatto the reactor was turned off and the catalyst allowed to cool under thecontinuing hydrogen flow.

Testing of the activated catalyst was as follows: —

At the end of activation, the catalyst was allowed to cool below 130° C.when the hydrogen flow was replaced by a synthesis gas (a mixture ofhydrogen, carbon monoxide and nitrogen) supplied from a cylinderproduced by differential component pressures flowing at a GHSV=1800 hr-1and the system slowly pressurised to 430 psig.

The temperature of the reactor was then slowly increased and theperformance of the catalyst producing Fischer Tropsch products wasmonitored.

Hours on GHSV Temperature Conversion Selectivity stream (hr) (hr⁻¹) (°C.) (mole %) to >C5 18.5 1800 203 37.4 82.2 91.0 1800 208 36.6 76.8 1211800 208 35.0 76.5

EXAMPLE 3 TESTING OF STANDARD CATALYST

10 ml (14.3 g) of “as received” Engelhard catalyst B958-30 was chargedto a fixed bed reactor and activated using the method previouslydescribed in Example 2.

Testing of the activated catalyst was again performed using the methodsdescribed in Example 2.

Hours on GHSV Temperature Conversion Selectivity stream (hr) (hr⁻¹) (°C.) (mole %) to >C5 8.0 1250 186 15.7 79.6 89.5 1250 206 27.9 74.9 125.51250 207 25.2 73.8

1-19. (canceled)
 20. Modified catalyst composition containing a supportand a Fischer-Tropsch metal for the conversion of syngas to liquidhydrocarbons, characterised in that a silylating compound modifier isadded to the said catalyst composition.
 21. Catalyst compositionaccording to claim 20 wherein the silylating compound is added duringthe catalyst preparation or during a post-treatment stage, preferablyduring a post-treatment stage.
 22. Catalyst composition according toclaim 20 wherein the silylating compound is chosen amongst organosiliconcompounds.
 23. Catalyst composition according to claim 22 wherein thesilylating compound is chosen amongst trimethyl silicon compounds, mostpreferably chosen amongst trimethylsilyl chloride, bis(trimethylsily)trifluoroacetamide,N-methyl-N-(trimethylsilyl)trifluoroacetamide, and mixtures thereof. 24.Catalyst composition according to claim 23 wherein the silyatingcompound is bis (trimethylsilyl)trifluoroacetamide.
 25. Catalystcomposition according to claim 20 wherein the Fischer-Tropsch metal is aGroup VIII metal preferably selected from iron, cobalt, ruthenium andnickel as well as molybdenum, tungsten, rhenium and the like. 26.Catalyst composition according to claim 25 wherein the Fischer-Tropschmetal is iron and/or cobalt.
 27. Catalyst composition according to claim20 wherein the support is chosen amongst alumina, silica, titania, zincoxide or mixtures thereof, preferably zinc oxide.
 28. Catalystcomposition according to claim 20 containing from 0.1 to 20 wt % cobalt(wrt support) supported on an inorganic oxide having a surface area ofless than 100 m²/g, and a promoter chosen from ruthenium, platinum orpalladium (when not the primary catalyst metal), aluminium, rhenium,hafnium, cerium, lanthanum and zirconium, the said promoter beingpresent in amounts less than the cobalt and with a promoter:metal ratioby weight of at least 1:10.
 29. Process for the conversion of syngas toliquid hydrocarbons in the presence of a modified supportedFischer-Tropsch catalyst composition according to claim
 20. 30. Processfor preparing a Fischer-Tropsch catalyst comprising a Fischer-Tropschmetal on a support, characterised by the catalyst being modified with asilylating compound.
 31. Process according to claim 30, whereinsilylating compound is added during the catalyst preparation or during apost-treatment stage, preferably during a post-treatment stage. 32.Process according to claim 30, wherein the silylating compound is chosenamongst organosilicon compounds.
 33. Process according to claim 32wherein the silylating compound is chosen amongst trimethyl siliconcompounds, most preferably chosen amongst trimethylsilyl chloride, bis(trimethylsilyl)trifluoroacetamide,N-methyl-N-(trimethylsilyl)trifluoroacetamide, and mixtures thereof. 34.Process according to claim 33 wherein the silylating compound is bis(trimethylsilyl)trifluoroacetamide.
 35. Process according to claim 30,wherein the Fischer-Tropsch metal is a Group VIII metal preferablyselected from iron, cobalt, ruthenium and nickel as well as molybdenum,tungsten, rhenium and the like.
 36. Process according to claim 35wherein the Fischer-Tropsch metal is iron and/or cobalt.
 37. Processaccording to claim 30, wherein the support is chosen amongst alumina,silica, titania, zinc oxide or mixtures thereof, preferably zinc oxide.38. Process for the conversion of syngas to liquid hydrocarbons in thepresence of a modified supported Fischer-Tropsch catalyst compositionprepared according to claim 30.